EP0413192A1 - Method of making 1,1'-oxybis(3-nitro-5-Trifluoromethyl)benzene - Google Patents
Method of making 1,1'-oxybis(3-nitro-5-Trifluoromethyl)benzene Download PDFInfo
- Publication number
- EP0413192A1 EP0413192A1 EP90114684A EP90114684A EP0413192A1 EP 0413192 A1 EP0413192 A1 EP 0413192A1 EP 90114684 A EP90114684 A EP 90114684A EP 90114684 A EP90114684 A EP 90114684A EP 0413192 A1 EP0413192 A1 EP 0413192A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitro
- oxybis
- trifluoromethyl
- benzene
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- WHNAMGUAXHGCHH-UHFFFAOYSA-N 1-nitro-3-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC(C(F)(F)F)=C1 WHNAMGUAXHGCHH-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 benzene compound Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 9
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- QZADIXWDDVQVKM-UHFFFAOYSA-N 1,3-dinitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC(C(F)(F)F)=C1 QZADIXWDDVQVKM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001408 amides Chemical group 0.000 claims description 3
- NDZJSUCUYPZXPR-UHFFFAOYSA-N 1-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C(F)(F)F NDZJSUCUYPZXPR-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 4
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- RKLBCPTURHSIOJ-UHFFFAOYSA-N 1-fluoro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(F)=CC(C(F)(F)F)=C1 RKLBCPTURHSIOJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NLLHXVBITYTYHA-UHFFFAOYSA-N Nitrofor Chemical compound CCN(CC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O NLLHXVBITYTYHA-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Definitions
- 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene can be made by heating 3,5-dinitrobenzotrifluoride with an alkali metal fluoride in an organic solvent in the presence of water.
- the starting material for the process of this invention is a known and commercially available nitro benzotrifluoride compound having the formula: where each "X" is independently selected from NO2, Cl, F, and fixtures thereof.
- each "X" is independently selected from NO2, Cl, F, and fixtures thereof.
- "X" is NO2, i.e., the compound is 3,5-dinitrobenzotrifluoride, because that compound is more readily available and NO2 is a better leaving group.
- the nitrobenzotrifluoride compound is heated in the presence of water with an alkali metal fluoride which can be potassium fluoride, cesium fluoride, or a mixture thereof; potassium fluoride is preferred as it is less expensive.
- an alkali metal fluoride which can be potassium fluoride, cesium fluoride, or a mixture thereof; potassium fluoride is preferred as it is less expensive.
- Any organic solvent that will dissolve the starting material can be used, preferably at about 10 to about 50% solids. Examples of suitable solvents include dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidinone, sulfolane, methyl sulfone, dimethyl sulfoxide, and methyl sulfoxide.
- Amide solvents are preferred, and dimethyl formamide in particular is preferred, as it is inexpensive and is easy to purify and remove. At least 1/2 equivalent of water, based on the amount of the OBB, should be used.
- the reaction mixture is heated to a temperature of about 140 to about 210°C and the reaction can be followed on a gas chromatograph to determine when it is complete. Depending on the temperature, the reaction takes about 1 to about 24 hours.
- the product can be isolated by distilling off the solvent, extracting the product from water, and crystallizing. A yield greater than 50% can be expected.
- the corresponding benzamine compound 5,5′-oxybis (3-trifluoromethyl)-benzamine, can be prepared by reducing the two nitro groups on OBB to amine groups.
- the reduction reaction is a relatively simple reaction which can be performed in the presence of a reducing agent, such as a mixture of about 10 to about 50% by weight Fe+3 and about 1 to about 20% by weight HCl.
- a reducing agent such as a mixture of about 10 to about 50% by weight Fe+3 and about 1 to about 20% by weight HCl.
- Other useful reducing agents include palladium, ammonium sulfide, hydrazine, etc.
- the benzamine compound is useful in making polyimides, polyamide-imides, and polyamides.
- the polyimides can be prepared by well-known reactions of diamines with dianhydrides or tetracarboxylic acids, substituting the benzamine of this invention for a divine that would otherwise be used. Further information on those reactions can be found in the hereinabove referenced co-pending European Patent Application EP ... (Case A 180 EP).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Disclosed is a method of making 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene by heating a nitro benzofluoride compound having the formula
where "X" is selected from the group consisting of NO₂, Cl, F, and mixtures thereof with an alkali metal fluoride selected from the group consisting of potassium fluoride, cesium fluoride, and mixtures thereof in an organic solvent in the presence of water. The corresponding diamine, 5,5′-oxybis (3-trifluoromethyl)-benzamine, can be prepared by reducing the benzene compound.
Description
- Disclosed is a method of making 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene by heating 3,5-dinitro-benzotrifluoride. Also disclosed is the reduction of 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene to 5,5′-oxybis (3-trifluoromethyl) benzamine.
- In European Patent Application EP ... (Case A 180 EP), filed of even date by Occidental Chemical Corporation, titled "Novel Bis-M-Benzotrilfuoride Compounds", herein incorporated by reference, there is described the novel compound 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene (OBB), and the novel compound 5,5′-oxybis (3-trifluoromethyl)-benzamine, which is made by reducing OBB. The benzamine compound is useful in making polyimides, polyamides, polyamide-imides, and polyurethanes. Polyimides made using the benzamine compound have excellent electronic properties, particularly a high solubility in organic solvents and a low dielectric constant, which make them very useful in the electronics industries. In addition, they also have the properties that polyimides are noted for -- outstanding mechanical strength and excellent thermal and oxidative stability. It has been discovered that 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene
- That this reaction occurs is quite surprising because the activating groups, the two nitro groups and the single trifluoromethyl group on the 3,5-dinitrobenzotrifluoride, are not in the correct ring position for producing that product. That is, both nitro groups and trifluoromethyl groups are known to activate the ortho and para positions on the benzene ring, and, because they are meta in this compound, one would expect a poor reaction to occur even under harsh conditions. Actually, the reaction is a very good reaction and occurs under mild conditions (temperatures of less than 150°C).
- The starting material for the process of this invention is a known and commercially available nitro benzotrifluoride compound having the formula:
- In the preparation of 1,1′-oxybis(3-nitro-5-trifluoromethyl) benzene, according to this invention, the nitrobenzotrifluoride compound is heated in the presence of water with an alkali metal fluoride which can be potassium fluoride, cesium fluoride, or a mixture thereof; potassium fluoride is preferred as it is less expensive. Any organic solvent that will dissolve the starting material can be used, preferably at about 10 to about 50% solids. Examples of suitable solvents include dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidinone, sulfolane, methyl sulfone, dimethyl sulfoxide, and methyl sulfoxide. Amide solvents are preferred, and dimethyl formamide in particular is preferred, as it is inexpensive and is easy to purify and remove. At least 1/2 equivalent of water, based on the amount of the OBB, should be used. The reaction mixture is heated to a temperature of about 140 to about 210°C and the reaction can be followed on a gas chromatograph to determine when it is complete. Depending on the temperature, the reaction takes about 1 to about 24 hours. The product can be isolated by distilling off the solvent, extracting the product from water, and crystallizing. A yield greater than 50% can be expected.
- The corresponding benzamine compound, 5,5′-oxybis (3-trifluoromethyl)-benzamine, can be prepared by reducing the two nitro groups on OBB to amine groups. The reduction reaction is a relatively simple reaction which can be performed in the presence of a reducing agent, such as a mixture of about 10 to about 50% by weight Fe⁺³ and about 1 to about 20% by weight HCl. Other useful reducing agents include palladium, ammonium sulfide, hydrazine, etc.
- The benzamine compound is useful in making polyimides, polyamide-imides, and polyamides. The polyimides can be prepared by well-known reactions of diamines with dianhydrides or tetracarboxylic acids, substituting the benzamine of this invention for a divine that would otherwise be used. Further information on those reactions can be found in the hereinabove referenced co-pending European Patent Application EP ... (Case A 180 EP).
- The following examples further illustrate this invention.
- To a 500 ml round bottom flask was charged 3,5-dinitrobenzotrifluoride (25.1 g.), potassium fluoride (21.2 g.), water (2.4 ml.), and dimethylformamide (DMF, 125 ml.). The reaction was heated to 160°C for 24 hours. The reaction mixture was diluted with water (400 ml.) and extracted with ether (3 times with 150 ml.). The ether was dried with magnesium sulfate and cooled to 5°C. The solid was collected and hexane added to the filtrate until the filtrate was cloudy. The filtrate was cooled to 5°C and the resulting solid collected to give a total of 11.3 g (53.8% yield) of the desired 1,1-oxybis(3-nitro-5-trifluoromethyl )benzene.
- The following experiment was conducted to determine if the other leaving groups could be used in place of nitro for the preparation of 1,1-oxybis(3-nitro-5-trifluoromethyl)benzene. To a solution of 3-fluoro-5-nitrobenzotrifluoride, isolated by distillation from the mother liquor of Example 1, in DMF (5 ml.) was added potassium fluoride (0.7 g.). The suspension was heated to 150°C and 2 drops of water were added. The reaction progress was monitored by gas chromatography (GC). After 7 hours, GC analysis indicated that a 0.17:1 mixture of 1,1-oxybis(3-nitro-5-trifluoromethyl)benzene to the starting fluoride had been obtained. This ratio increased to 2.1:1 after heating for 17.5 hours.
Claims (12)
1. A method of making 1,1′-oxybis (3-nitros-trifluoromethyl)-benzene comprising heating a nitro-benzotrifluoride compound having the formula
where each "X" is independently selected from the group consisting of NO₂, Cl, F, and mixtures thereof, with an alkali metal fluoride selected from the group consisting of potassium fluoride, cesium fluoride, and mixtures thereof in an organic solvent in the presence of water.
2. A method according to Claim 1 wherein X is NO₂.
3. A method according to Claim 1 or 2 wherein said alkali metal fluoride is potassium fluoride.
4. A method according to any one of Claims 1 to 3 wherein said nitro benzotrifluoride is heated at a temperature of about 140 to about 210°C.
5. A method according to any one of Claims 1 to 4 wherein said organic solvent is an amide.
6. A method according to Claim 5 wherein said organic solvent is dimethyl formamide.
7. A method according to Claim 1 including the additional last step of distilling off said organic solvent and crystallizing said 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene.
8. A method according to Claim 1 including the additional last step of reducing said 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene to 1,1′-oxybis (3-nitro-5-trifluoromethyl )-benzamine.
9. A method according to Claim 8 wherein said reduction is performed by heating in the presence of about 10 to about 50% by weight Fe⁺³ and about 1 to about 20% by weight HCl.
10. A method of making 1,1′-oxybis (3-nitro-5-trifluoromethyl )-benzene comprising heating 3,5-dinitro-benzotrifluoride to a temperature of about 140 to about 210°C with potassium fluoride in an amide solvent in the presence of at least 1/2 equivalent of water, based on the amount of said 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene.
11. A method of making 5,5′-oxybis(3trifluoromethyl)-benzamine comprising
(1) heating a nitro-benzotrifluoride compound having the formula
where "X" is selected from the group consisting of NO₂, Cl, F, and mixtures thereof, with an alkali metal fluoride selected from the group consisting of potassium fluoride, cesium fluoride, and mixtures thereof in an organic solvent in the presence of water; and
(2) reducing said 1,1′-oxybis (3-nitro-5-trifluoromethyl)-benzene to 5,5′-oxybis (3-trifluoromethyl)-benzamine.
12. A method according to Claim 11 wherein X˝ is NO₂.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US394986 | 1989-08-17 | ||
| US07/394,986 US4990670A (en) | 1989-08-17 | 1989-08-17 | Method of making 1,1'-oxybis (3-nitro-5-trifluoromethyl)-benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0413192A1 true EP0413192A1 (en) | 1991-02-20 |
| EP0413192B1 EP0413192B1 (en) | 1994-02-16 |
Family
ID=23561212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90114684A Expired - Lifetime EP0413192B1 (en) | 1989-08-17 | 1990-07-31 | Method of making 1,1'-oxybis(3-nitro-5-Trifluoromethyl)benzene |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4990670A (en) |
| EP (1) | EP0413192B1 (en) |
| JP (1) | JPH0383952A (en) |
| CA (1) | CA2021725A1 (en) |
| DE (1) | DE69006659D1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0495425A2 (en) * | 1991-01-14 | 1992-07-22 | Occidental Chemical Corporation | Preparation of diphenyl ether |
| EP0509241A2 (en) * | 1991-03-15 | 1992-10-21 | Occidental Chemical Corporation | A novel method for ether formation |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2021753A1 (en) * | 1989-08-17 | 1991-02-18 | Jeffrey S. Stults | Bis-m-benzotrifluoride compounds |
| US5484879A (en) * | 1990-12-17 | 1996-01-16 | Occidental Chemical Corporation | Polyimides containing fluorine |
| JP2008251687A (en) | 2007-03-29 | 2008-10-16 | Toshiba Corp | Printed circuit board, and electronic equipment equipped with this |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673123A (en) * | 1969-03-21 | 1972-06-27 | Bayer Ag | 2,2{40 ,4,4{40 -tetrachloro-5,5{40 -diamino-diphenyl ether |
| EP0193358A1 (en) * | 1985-02-22 | 1986-09-03 | MITSUI TOATSU CHEMICALS, Inc. | Method of preparing 3,3'-dinitrodiphenyl ether |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3063962A (en) * | 1960-06-06 | 1962-11-13 | Universal Oil Prod Co | Polyolefins containing 4, 4'- and 2, 4'-dialkylaminodiphenyl ethers as antioxidants |
| US3140316A (en) * | 1960-06-23 | 1964-07-07 | Harshaw Chem Corp | Manufacture of diaminodiphenylether |
| BE628133A (en) * | 1962-02-08 | |||
| US3290377A (en) * | 1963-07-11 | 1966-12-06 | Koppers Co Inc | Catalytic reduction of nitro compounds to amines |
| DE1290147B (en) * | 1967-08-04 | 1969-03-06 | Bayer Ag | Process for the preparation of 4,4-Dinitrodiphenylethern |
| US4179461A (en) * | 1975-10-21 | 1979-12-18 | Bayer Aktiengesellschaft | Process for the preparation of diphenyl ethers |
| JPS5949217B2 (en) * | 1978-08-10 | 1984-12-01 | 三井東圧化学株式会社 | Method for producing substituted diphenyl ether |
| US4484008A (en) * | 1982-09-30 | 1984-11-20 | Ppg Industries, Inc. | Process improvement for diphenyl ether production |
-
1989
- 1989-08-17 US US07/394,986 patent/US4990670A/en not_active Expired - Fee Related
-
1990
- 1990-07-23 CA CA002021725A patent/CA2021725A1/en not_active Abandoned
- 1990-07-31 EP EP90114684A patent/EP0413192B1/en not_active Expired - Lifetime
- 1990-07-31 DE DE90114684T patent/DE69006659D1/en not_active Expired - Lifetime
- 1990-08-09 JP JP2211452A patent/JPH0383952A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673123A (en) * | 1969-03-21 | 1972-06-27 | Bayer Ag | 2,2{40 ,4,4{40 -tetrachloro-5,5{40 -diamino-diphenyl ether |
| EP0193358A1 (en) * | 1985-02-22 | 1986-09-03 | MITSUI TOATSU CHEMICALS, Inc. | Method of preparing 3,3'-dinitrodiphenyl ether |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OPF JAPAN, unexamined applciations, C field, vol. 4, no. 54, April 23, 1980 THE PATENT OFFICE JAPANESE GOVERNMENT page 18 C 8 * JP - A - 55 -24 125 (MITSUI TOATSU ) * * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0495425A2 (en) * | 1991-01-14 | 1992-07-22 | Occidental Chemical Corporation | Preparation of diphenyl ether |
| EP0495425A3 (en) * | 1991-01-14 | 1993-04-21 | Occidental Chemical Corporation | Preparation of diphenyl ether |
| EP0509241A2 (en) * | 1991-03-15 | 1992-10-21 | Occidental Chemical Corporation | A novel method for ether formation |
| EP0509241A3 (en) * | 1991-03-15 | 1992-11-19 | Occidental Chemical Corporation | A novel method for ether formation |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2021725A1 (en) | 1991-02-18 |
| US4990670A (en) | 1991-02-05 |
| DE69006659D1 (en) | 1994-03-24 |
| JPH0383952A (en) | 1991-04-09 |
| EP0413192B1 (en) | 1994-02-16 |
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